This invention relates to liquid phase oxidation of halogen substituted alkyl aromatic compounds. In particular,.the invention relates to liquid phase oxidation of chloro-ortho-xylene to produce chlorophthalic acid which can be dehydrated to produce chlorophthalic anhydride.
Liquid phase oxidation has long been used to produce dicarboxylic acids from dialkyl benzenes. Of particular interest has been the oxidation of dimethyl benzene (xylene) to phthalic acid, especially the oxidation of para-xylene to terephthalic acid, which is used in the production of polybutylene terephthalate. The liquid phase oxidation of xylene to phthalic acid requires the use of a catalyst, typically a cobalt/manganese/bromide catalyst system, and is generally performed in a carboxylic acid solvent such as acetic acid. The catalyst system may be augmented by the use of a co-catalyst such as zirconium, hafnium or cerium. Phthalic acid is an easily isolable solid, which can be filtered out of the reaction mixture.
Liquid phase oxidation, using a cobalt/manganese/bromide catalyst system and a carboxylic acid solvent, has also been applied to halogenated xylene with some success. The oxidation of the halogenated xylene is more difficult than the oxidation of xylene due to presence of a halogen, which is an electron withdrawing substituent, on the benzene ring. The greater difficulty in oxidation results in a lower reaction selectivity and a larger amount of partial oxidation and side products than seen in the liquid phase oxidation of xylene under similar conditions. Additionally, halogenated phthalic acid is difficult to separate from the partial oxidation and side products, even by distillation. Thus it is clear that in order for a method of halogenated xylene liquid phase oxidation to be commercially successful the reaction yield and the reaction selectivity must be very high. Optimally, for a useful commercial process, the reaction selectivity should be high enough to result in only negligible amounts of partial oxidation and side products thus removing the need for isolation of halophthalic acid.
A method for the manufacture of chlorophthalic acid comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of chloro-ortho-xylene, about 0.25 to about 2 mole percent, based on the chloro-ortho-xylene, of a cobalt source, about 0.1 to about 1 mole percent, based on the chloro-ortho-xylene, of a manganese source, about 0.01 to about 0.1 mole percent, based on the chloro-ortho-xylene, of a source of a metal selected from zirconium, hafnium and mixtures thereof, and about 0.02 to about 0.05 mole percent, based on the chloro-ortho-xylene, of a bromide source; maintaining the reaction mixture at a pressure of at least about 1600 kilopascals (KPa) and at a temperature of about 150xc2x0 C. to about 170xc2x0 C.; introducing a molecular oxygen containing gas to the reaction mixture at a rate of at least about 1.0 normal m3 of gas/hour per kilogram (kg) of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas from the reaction mixture, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas; maintaining the introduction of the molecular oxygen containing gas until the off gas oxygen concentration exceeds about 3 percent by volume of the off gas; modifying the introduction of the molecular oxygen containing gas to maintain the off gas oxygen concentration below about 5 percent by volume of the off gas; and maintaining the modified introduction of the molecular oxygen containing gas for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid.
In another aspect, the method for the manufacture of chlorophthalic acid comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of chloro-ortho-xylene, about 0.8 to about 1.2 mole percent, based on the chloro-ortho-xylene, of a cobalt source, about 0.4 to about 0.6 mole percent, based on the chloro-ortho-xylene, of a manganese source, about 0.04 to about 0.06 mole percent, based on the chloro-ortho-xylene, of a source of an ionic metal selected from zirconium, hafnium and mixtures thereof, and less than about 0.04 mole percent, based on the chloro-ortho-xylene, of a bromide source; maintaining the reaction mixture at a pressure of at least about 1600 KPa and at a temperature of about 150xc2x0 C. to about 170xc2x0 C.; introducing air to the reaction mixture at a rate of at least about 1.0 normal m3 of oxygen/kg of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas; maintaining the introduction of the air until the off gas oxygen-concentration exceeds about 3 percent by volume of the off gas; modifying the introduction of air so as to maintain the off gas oxygen concentration below about 5 percent by volume of the off gas; and maintaining the modified introduction of air for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid.
In another embodiment, a method for the manufacture of chlorophthalic anhydride comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of a chloro-ortho-xylene, about 0.25 to about 2 mole percent, based on the chloro-ortho-xylene, of a cobalt source, about 0.1 to about 1 mole percent, based on the chloro-ortho-xylene, of a manganese source, about 0.01 to about 0.1 mole percent, based on the chloro-ortho-xylene, of a source of a metal selected from zirconium, hafnium and mixtures thereof, and about 0.02 to about 0.05 mole percent, based on the chloro-ortho-xylene, of a bromide source; maintaining the reaction mixture at a pressure of at least about 1600 KPa and at a temperature of about 150xc2x0 C. to about 170xc2x0 C.; introducing a molecular oxygen containing gas to the reaction mixture at a rate of at least about 1.0 normal m3 of oxygen/kg of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas; maintaining the introduction of the molecular oxygen containing gas until the off gas oxygen concentration exceeds about 3 percent by volume of the off gas; modifying the introduction of the molecular oxygen containing gas to maintain the off gas oxygen concentration below about 5 percent by volume of the off gas; maintaining the modified introduction of the molecular oxygen containing gas for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid; removing the acetic acid and any water formed as a result of the reaction, by distillation; and dehydrating the chlorophthalic acid to form chlorophthalic anhydride.
In another aspect, the method for the manufacture of chlorophthalic anhydride comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of a chloro-ortho-xylene, about 0.8 to about 1.2 mole percent, based on the chloro-ortho-xylene, of cobalt acetate or cobalt acetate hydrate, about 0.4 to about 0.6 mole percent, based on the chloro-ortho-xylene, of manganese acetate or manganese acetate hydrate, about 0.04 to about 0.06 mole percent, based on the chloro-ortho-xylene, of zirconium acetate or zirconium acetate hydrate, and less than about 0.04 mole percent, based on the chloro-ortho-xylene, of sodium bromide or hydrogen bromide; maintaining the reaction mixture-at a pressure of at least about 1600 KPa and at a temperature of about 150xc2x0 C. to about 170xc2x0 C.; introducing air to the reaction mixture at a rate of at least about 1.0 normal m3 of oxygen/kg of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas, maintaining the introduction of air until the off gas oxygen concentration exceeds about 3 percent by volume of the off gas; modifying the introduction of air to maintain the off gas oxygen concentration below about 5 percent by volume of the off gas and maintaining the modified introduction of air for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid; removing the acetic acid and any water formed as a result of the reaction by distillation; recycling the acetic acid; and dehydrating the chlorophthalic acid to form chlorophthalic anhydride.
In another embodiment, a method for the manufacture of polyetherimide comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of a chloro-ortho-xylene, about 0.25 to about 2 mole percent, based on the chloro-ortho-xylene, of a cobalt source, about 0.1 to about 1 mole percent, based on the chloro-ortho-xylene, of a manganese source, about 0.01 to about 0.1 mole percent, based on the chloro-ortho-xylene, of a source of metal selected from zirconium, hafnium and mixtures thereof, about 0.02 to about 0.05 mole percent, based on the chloro-ortho-xylene, of a bromide source; maintaining the reaction mixture at a pressure of at least about 1600 KPa and a temperature of about 150xc2x0 C. to about 170xc2x0 C.; introducing a molecular oxygen containing gas to the reaction mixture at a rate of at least about 1.0 normal m3 of oxygen/kg of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas; maintaining the introduction of the molecular oxygen containing gas until the off gas oxygen concentration exceeds about 3 percent by volume of the off gas; modifying the introduction of the molecular oxygen containing gas to maintain the off gas oxygen concentration below about 5 percent by volume of the off gas and maintaining the modified introduction of the molecular oxygen containing gas for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid with less than about 200 parts per million (ppm) of chlorophthalide removing the acetic acid and any water formed as a result of the reaction by distillation; dehydrating the chlorophthalic acid i to form chlorophthalic anhydride; reacting the chlorophthalic anhydride with 1,3-diaminobenzene to form bis(chlorophthalimide) (II) 
; and reacting bis(chlorophthalimide) (II) with an alkali metal salt of a dihydroxy substituted aromatic hydrocarbon having the formula (IV)
OHxe2x80x94A2OH(IV),
wherein A2 is a divalent aromatic hydrocarbon radical to form the polyetherimide.
A method for the manufacture of chlorophthalic acid comprises forming a reaction mixture comprising a mixture of about 5 to about 3 parts by weight of acetic acid to 1 part by weight of a chloro-ortho-xylene, about 0.25 to about 2 mole percent, based on the chloro-ortho-xylene, of a cobalt source, about 0.1 to about 1 mole percent, based on the chloro-ortho-xylene, of a manganese source, about 0.01 to about 0.1 mole percent, based on the chloro-ortho-xylene, of a source of a metal selected from zirconium, hafnium and mixtures thereof, and about 0.02 to about 0.05 mole percent, based on the chloro-ortho-xylene, of a bromide source. The reaction mixture is maintained at a pressure of at least about 1600 KPa and at a temperature of about 150xc2x0 C. to about 170xc2x0 C. A molecular oxygen containing gas is introduced to the reaction mixture at a rate of at least about 1.0 normal m3 of oxygen containing gas/hour per kg of chloro-ortho-xylene in the reaction mixture to create an oxygen containing off gas, wherein the off gas oxygen concentration is less than about one percent by volume of the off gas. The introduction of the molecular oxygen containing gas is maintained until the off gas oxygen concentration exceeds about 3 percent by volume of the off gas and then the introduction of the molecular oxygen containing gas is modified so as to maintain the off gas oxygen concentration below about 5 percent by volume. The modified introduction of the molecular oxygen containing gas is maintained for a time sufficient to provide at least about 90 percent conversion of the chloro-ortho-xylene to chlorophthalic acid.
Using the method for manufacture of chlorophthalic acid and anhydride described herein, the high yield synthesis of high purity chlorophthalic acid and anhydride is possible on a large scale employing hundreds of kilograms of chloro-ortho-xylene by liquid phase oxidation in the presence of about 0.25 to about 2 mole percent (mol %) of a cobalt source, about 0.1 to about 1 mol % of a manganese source, about 0.01 to about 0.1 mol % of a source of a metal selected from zirconium; hafnium and mixtures thereof, and about 0.02 to about 0.05 mol % of a bromide source. Applicants have discovered that in large scale liquid phase oxidations employing chloro-ortho-xylene the amount of bromide can have a significant impact on the amount of impurities present in the final product. The use of decreasing molar percentages of bromide result in a product, either chlorophthalic acid or anhydride, with a decreased level of impurities such as chlorophthalide. While the reasons for this phenomenon are not clearly understood it is contemplated that even lower levels of bromide, molar percentages less than about 0.02, may be useful in producing high purity chlorophthalic acid or anhydride in even larger scale liquid phase oxidations such as those employing thousands of kilograms of chloro-ortho-xylene.
Chloro-ortho-xylene suitable for use in the oxidation has the structure (IV) 
The chlorine substituent may be in the 3 position (the 3-isomer) or in the 4 position (the 4-isomer). The chloro-ortho-xylene used in the liquid-phase oxidation may also be a mixture of the 3-isomer and the 4-isomer.
The liquid phase oxidation preferably employs acetic acid as a solvent although other lower carboxylic acids may be employed. Preferably glacial acetic acid is used but acetic acid with a water content of up to 3 percent may be employed. Typically the acetic acid is present in an amount of 5 to 3 parts by weight to 1 part by weight of chloro-ortho-xylene.
Suitable molecular oxygen containing gases include gases or combinations of gases which are a source of molecular oxygen(O2), for example 100 percent oxygen and mixtures of oxygen with an inert gas with a sufficient concentration of oxygen to effect oxidation. Sufficient oxygen concentrations typically are greater than or equal to about 6 percent oxygen, preferably greater than or equal to about 15 percent, more preferably greater than or equal to about 20 percent. Mixtures with greater than or equal to about 50 percent oxygen may also be used. As will be appreciated by one of skill in the art, the concentration of oxygen may affect the rate of the reaction. A preferred molecular oxygen containing gas is air.
Useful cobalt, manganese, bromide, zirconium, and hafnium sources are those sources which are soluble in acetic acid. Cobalt, manganese, zirconium and hafnium sources that may be used include the metals themselves or any of their salts, complexes or compounds. These include, but are not limited to, acetates, citrates, stearates, napthenates, acetylacetonates, benzoylacetonates, carbonates, sulfates, bromides, chlorides, fluorides, nitrates, hydroxides, alkoxides, nitrides, triflates, hydrates of the foregoing and mixtures of the foregoing. Preferably the cobalt in the cobalt source is in a +2 or +3 oxidation state. Preferably the manganese in the manganese source is in a +2 or +3 oxidation state. Examples of bromide sources include, but are not limited to, bromine, hydrogen bromide, a metal-bromide salt such as sodium bromide and organic bromides. Examples of organic bromides include tetrabromoethane, ethyl bromide, ethylene bromide, bromoform, xylyl bromide, xylylene bromide and mixtures comprising at least one of the organic bromides.
The mole percent of the cobalt, manganese, zirconium, hafnium, and bromide sources are based on the amount of chloro-ortho-xylene present at the beginning of the reaction. The cobalt source is generally present in amounts of about 0.25 to about 2 mol %. Preferably, the cobalt source is present in an amount of less than about 1.2 mol %. In addition, it is also preferable for the cobalt source to be present in an amount greater than or equal to about 0.5 mol %, and more preferably in an amount greater than or equal to about 0.8 mol %. It is particularly preferred for the amount of the cobalt source to be about 1 mol %.
The manganese source is present in amounts of about 0.1 to about 1 mol %. Preferably, the manganese source is present in an amount less than or equal to about 0.6 mol %. Additionally, it is also preferable for the manganese source to be present in an amount greater than or equal to about 0.3 mol %, more preferably greater than or equal to about 0.4 mol %. In a particularly preferred embodiment, the manganese source is present in an amount of about 0.5 mol %.
The bromide source is generally present in amounts of about 0.02 to about 0.05 mol %. Preferably, the amount of the bromide source is less than or equal to 0.04 mol %, and most preferably less than or equal to 0.03 mol %.
The zirconium source, hafnium source or mixture thereof is generally present in amounts of about 0.01 to about 0.1 mol %. Preferably, the zirconium source, hafnium source or mixture thereof is present in an amount less than or equal to about 0.06 mol %. Additionally it is also preferable for the zirconium source, hafnium source or mixture thereof to be present in an amount greater than or equal to about 0.03 mol %, more preferably greater than 0.04 mol %. In a particularly preferred embodiment, the zirconium source, hafnium source or mixture thereof is present in an amount of about 0.05 mol %.
In an exemplary process, the chlorophthalic acid may be produced by combining chloro-ortho-xylene, cobalt source; manganese source; bromide source, and zirconium source, hafnium source or mixture thereof in acetic acid in a reaction vessel. The reaction vessel is established at a pressure of greater than about 1600 Kpa and the desired reaction temperature, generally under an inert atmosphere such as nitrogen or argon. The temperature of the reaction is typically about 150xc2x0 C. to about 170xc2x0 C. The molecular oxygen containing gas is introduced to the reaction mixture and the flow of the molecular oxygen containing gas is maintained at a rate that creates an oxygen containing off gas with an oxygen concentration of less than 1 percent by volume. The oxygen concentration of the off gas may be determined by paramagnetic transduction oxygen analysis or other method known in the art. Useful flow rates are typically greater than or equal to 1.0 normal cubic meter (m3)/hour per kilogram (kg) of chloro-ortho-xylene. A normal cubic meter is defined as cubic meter under standard temperature and pressure conditions. Preferably the reaction mixture, is agitated using standard methods such as mechanical stirring. The flow of the molecular oxygen containing gas continues until the off gas oxygen concentration exceeds about 3 percent by volume, indicating a slowing of the reaction. Once the off gas oxygen concentration exceeds about 3 percent by volume the flow of the molecular oxygen containing gas is modified so as to maintain the off gas oxygen concentration below about 5 percent by volume and the temperature of the reaction may be increased. It is preferable, however, for the temperature to remain below about 200xc2x0 C. The flow of the molecular oxygen containing gas may be modified in several ways. The molecular oxygen containing gas may be diluted with an inert gas so as to decrease the oxygen concentration in the molecular oxygen containing gas, the flow rate of the molecular oxygen containing gas may be decreased, the source of the molecular oxygen containing gas may be changed so as to employ a molecular oxygen containing gas with a lower oxygen concentration or these methods may be combined so as to maintain the oxygen concentration of the off gas below about 5 percent by volume. The modified flow of the molecular oxygen containing gas is continued until at least about 90 percent of chloro-ortho-xylene has been converted to chlorophthalic acid, preferably until greater than about 95 percent has been converted. The amount of conversion achieved in the reaction can readily be determined through the use of gas chromatography, mass spectrometry or other methods known in the art. In our experience, the amount of time required to reach 90 percent conversion of chloro-ortho-xylene is about 3 to about 6 hours.
After the reaction reaches the desired level of completion, the chlorophthalic acid may be recovered as chlorophthalic acid or chlorophthalic anhydride. Many applications such as pharmaceutical applications and polymer synthesis require chlorophthalic acid and chlorophthalic anhydride with a high degree of purity. Such high degree of purity may be achieved by the method described herein. Impurities produced include chlorobenzoic acid, phthalic anhydride and chlorophthalide. In fact, chlorophthalide acid and chlorophthalic anhydride containing less than about 600 ppm of chlorophthalide (all chlorophthalide isomers), preferably less than about 500 ppm of chlorophthalide, and more preferably less than about 400 ppm of chlorophthalide is readily achievable. Additionally, chlorophthalic acid and chlorophthalic anhydride containing less than about 1% by weight of phthalic anhydride and chlorobenzoic acid may also be achieved. Chlorotoluic acids and dichlorophthalic acids are typically not detected.
Most of the acetic acid and water produced in the reaction can be removed by distillation at approximately atmospheric pressure, typically by heating to about 200xc2x0 C. at 200 KPa. The acetic acid and water are removed as a vapor and condensed. The water may then be removed from the acetic acid and the acetic acid may be recycled. Some dehydration of the chlorophthalic acid to form chlorophthalic anhydride may occur simultaneously with the removal of acetic acid and water. Furthermore, the removal of acetic acid and water may be combined with dehydration to form a single step. Dehydration is typically done thermally by distillation under vacuum at an elevated temperature allowing dehydration and isolation of the chlorophthalic anhydride from any remaining acetic acid and water to occur simultaneously. Dehydration may also be carried out by other chemical reactions well known to those skilled in the art, such as treatment with acetic anhydride. After distillation the chlorophthalic anhydride is typically greater than about 98 percent pure and preferably greater than 99 percent pure. Chlorophthalic anhydrides of high purity are used in the synthesis of polyetherimide.
Polyetherimides are high heat engineering plastics having a variety of uses. One route for the synthesis of polyetherimides proceeds through a bis(4-chlorophthalimide) having the following structure (I) 
wherein X is a divalent alkylene, cycloalkylene, or arylene moiety. The bis(4-chlorophthalimide) wherein X is a 1,3-phenyl group (II) is particularly useful. 
Bis(chlorophthalimide)s (I) and (II) are typically formed by the condensation of diamines, such as 1,3-diaminobenzene with anhydrides, such as 4-chlorophthalic anhydride (III): 
Polyetherimides may be synthesized by the reaction of the bis(chlorophthalimide) with an alkali metal salt of a dihydroxy substituted aromatic hydrocarbon in the presence or absence of phase transfer catalyst. Suitable phase transfer catalysts are disclosed in U.S. Pat. No. 5,229,482. Suitable dihydroxy substituted aromatic hydrocarbons include those having the formula (IV)
OHxe2x80x94A2OH(IV),
wherein A2 is a divalent aromatic hydrocarbon radical. Suitable A2 radicals include m-phenylene, p-phenylene, 4,4xe2x80x2-biphenylene, 4,4xe2x80x2-bi(3,5-dimethyl)phenylene, 2,3-bis(4-phenylene)propane and similar radicals such as those disclosed by name or formula in U.S. Pat. No. 4,217,438.
The A2 radical preferably has the formula (V)
xe2x80x94A3xe2x80x94Yxe2x80x94A4xe2x80x94(V)
wherein each of A3 and A4 is a monocyclic divalent aromatic hydrocarbon radical and Y is a bridging hydrocarbon radical in which one or two atoms separate A3 from A4. The free valence bonds in formula (V) are usually in the meta or para positions of A3 and A4 in relation to Y. A3 and A4 may be substituted phenylene or hydrocarbon-substituted derivative thereof, illustrative substituents (one or more) being alkyl and alkenyl. Unsubstituted phenylene radicals are preferred. Both A3 and A4 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
The bridging radical, Y, is one in which one or two atoms, preferably one, separate A3 from A4. Illustrative radicals of this type are methylene, cyclohexylmethylene, 2-(2,2,1)-bicycloheptylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene, and adamantylidene. The preferred radical of formula (IV) is 2,2-bis(4-phenylene)propane radical which is derived from bisphenol A and in which Y is isopropylidene and A3 and A4 are each p-phenylene.
It is clear to one of ordinary skill in the art that any impurities present in the chlorophthalic anhydride will be carried through to subsequent steps in the polyetherimide synthesis. The presence of significant levels of impurities in subsequent steps can interfere with polymerization and cause discoloration of the final product, polyetherimide.